CN1723872B

CN1723872B - Oil-in-water emulsified composition

Info

Publication number: CN1723872B
Application number: CN2005100850863A
Authority: CN
Inventors: 河上恭子; 冈田让二
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 2004-07-20
Filing date: 2005-07-20
Publication date: 2010-12-15
Anticipated expiration: 2025-07-20
Also published as: KR20060053893A; EP1627623A1; JP2006028109A; CN1723872A; KR101422276B1; EP1627623B1; TW200615005A; DE602005001478D1; DE602005001478T2; US20060018866A1; TWI379692B

Abstract

The present invention provides an oil-in-water emulsified composition containing; (A) ester oil which is in liquid state at 25 DEG C (B) sphingosines represented by the formula (1) (wherein, R 1 represents hydrocarbon group which may have a substituent; Y represents a methylene group, a methine group or an oxygen atom; X 1 ,X 2 and X 3 are H, OH or an acetoxy group; X 4 represents H, an acetyl group or the like; R 2 and R 3 are H, OH and the like; R represents H or an amidino group; ''a'' stands for 2 or 3;) (C) an acid compound selected from the group consisting of inorganic acid or an organic acid having 5 or less carbon atoms, and (D) cholesterol or phytosterol, wherein the ratio of a liquid oil component containing Component (A) in the total amount of oil phase is 5 to 90 wt%.

Description

O/W emulsion composition

Technical field

The present invention relates to a kind of O/W emulsion composition that contains sphingosine class, cholesterol and aqueous ester oil and storage stability and use sense of touch excellence.

Background technology

At present, ester oil uses as the oil phase composition in emulsification composition, relaxes the oiliness of goods, and also mutual blended mixed agent is worked as composition that prescription contains.And be the material that has as the function of the dispersant of dissolving adjuvant such as organic component, pigment or spice or fixative, inorganic powder.Moreover, but the skin preparations for extenal use of known interpolation ester oil usually softening skin and make the stretching of skin good, impregnability is good and have moisture retention.Therefore, in order to improve the sense of touch of uses such as skin preparations for extenal use, in recent years, have and add the tendency that ester oil replaces wax or hydrocarbon ils.

But when adding to ester oil in the emulsification composition, surfactant dissolves is transferred to the oil phase in ester oil and from the surface, and the surface is disorderly and unstable, and emulsified state worsens.Its result causes the gloss disappearance on compositions surface etc., impairs outward appearance.Therefore, when using a large amount of surfactants and stably during emulsifying ester oil, can produce the problem of usability deteriorations such as be clamminess sense, moist feeling etc.Therefore think that stable interpolation ester oil is very difficult.

Therefore, the spy opens the 2001-220315 communique and discloses and a kind ofly contain the oil phase composition of polar oil with the dispersive cosmetic compositions of stable spherical-like morphology by not using surfactant to use the powder composition of water dispersible and non-oil-dispersing property, making.But lower alcohols such as ethanol make an addition in the said composition with high concentration, can not be applied in the non-alcohol prescription.Unavoidably will use and stockpile powder for containing the powder composition, powder composition precipitation must be vibrated during use during placement, cause use loaded down with trivial details.

Moreover, the spy opens the 2003-40731 communique and has also put down in writing a kind of by using polyoxy butylene polyglycereol monoalkyl (mono alkenyl) ether and polyglycereol mono fatty acid ester as hydrophilic surfactant, emulsifying polar oil stably, make it not produce aldehyde, to the emulsification composition of the excellent in stability of skin.But it is inadequate reducing amount of surfactant.

As mentioned above, also there is certain difficulty in the emulsification composition in order to improve use sense of touch or performance of keeping humidity, stably ester oil to be added to.

Summary of the invention

The invention provides a kind of O/W emulsion composition, it is characterized in that, contain following composition (A), (B), (C) and (D):

(A) be the ester oil of liquid down at 25 ℃;

(B) the sphingosine class of representing with general formula (1)

In the formula, R ¹Represent that available hydroxyl, carbonyl or the amino carbon number that replaces are 4～30 straight chain, side chain or cyclic saturated or undersaturated alkyl; Y represents methylene, methine or oxygen atom; X ¹, X ²And X ³Difference independent and expression hydrogen atom, hydroxyl or acetate; X ⁴Represent hydrogen atom, acetyl group or glyceryl, or form carbonyl with contiguous oxygen atom, still, when Y is methine, X ¹And X ²Any be hydrogen atom, another does not exist, and works as X ⁴When forming carbonyl, X ³Do not exist; R ²And R ³Difference independent and expression hydroxyl, methylol or acetate methyl; A R is independent respectively and be hydrogen atom or amidino groups, or represents to have the saturated or unsaturated alkyl of the straight or branched of the substituent total carbon atom number 1～8 that is selected from hydroxyl, hydroxy alkoxy base, alkoxyl and acetate; A represents 2 or 3 numeral; Dotted line is represented also can be unsaturated bond;

(C) be selected from mineral acid and the carbon number organic acid acid compound below 5;

(D) cholesterol or plant sterol,

With respect to all oil phase total amounts, the shared ratio of liquid oil sexual element that contains composition (A) is 5～90 weight %.

The specific embodiment

Even the present invention relates to the also emulsifying stably of a kind of interpolation ester oil, the O/W emulsion composition of storage stability, outward appearance and usability excellence.

Discoveries such as the inventor make sphingosine class and acid compound coexistence, both carry out neutralization reaction and form salt, the amino of sphingosine class is by cationization, bringing into play the effect of activating agent, the ceramide type of the easy crystallization of emulsifying stably, and various skin preparations for extenal use are studied.

The present invention worked as skin preparations for extenal use extensive use ester oil and time spent, sphingosine class and the cholesterol or the plant sterol of combination cationization, make profit surface stabilisation more firmly, and make with certain ratio that to contain at 25 ℃ in the oil phase be the liquid oil sexual element of liquid ester oil down, the ester oil of the emulsifying liquid that discovery can be stable and the invention finished thus.

O/W emulsion composition of the present invention is emulsifying ester oil stably, even do not contain surfactant, also can keep emulsified state steadily in the long term.Moreover the surface is glossy, has good surface appearance and excellent usability.

In O/W emulsion composition of the present invention, with the sphingosine class of general formula (1) expression be selected from mineral acid and the organic acid acid compound of carbon number below 5 forms salt by neutralization reaction, the sphingosine class works by cationization and as activating agent.And the present inventor thinks: by adding cholesterol, even contain ester oil in the oil phase, sphingosine class by cationization does not dissolve yet, transfers in the oil phase, but be prevalent in the profit surface, giving full play to the effect of surfactant, so can obtain stable emulsification composition.Good and the emulsified particles of emulsified state decomposes equably, thus the outward appearance of cosmetic glossy, seem very beautiful and excellent storage stability.Moreover, even said composition is except that also being stable by not adding surfactant the sphingosine class of cationization, so compare with common emulsification preparation, not only can reduce the amount of surfactant, and it is good to the adaptability of skin, has the usability that does not have oiliness or be clamminess, to the skin safety height.

Composition used herein (A) is to have mobile ester oil under the condition of 25 ℃ of 1 air pressure at the ester oil of the liquid under 25 ℃.In addition, the so-called ester oil among the present invention is by acid and dehydration of alcohols and the material that obtains wherein has the acid of carboxyl as acid with fatty acid, polyprotic acid, aminoacid etc.; The material that has hydroxyl with steroids such as lower alcohol, higher alcohol, polyhydric alcohol, cholesterol etc. judges whether to be ester oil by measuring saponification number or ester value usually as alcohol.Moreover, also contain refining vegeto-animal ester oil or specific UV absorbent etc. in the raw material.

Ester oil as the liquid of composition (A) under 25 ℃, for example, can enumerate isopropyl myristate, butyl myristate, isopropyl palmitate, Octanoic acid, hexadecyl ester, sad different cetyl, sad different stearyl ester, sad hexadecyl ester octadecyl ester mixture (cetostearyl セトステァリ Le), sad stearyl ester, the myristic acid isotridecanol, the different cetyl of myristic acid, the different stearyl ester of myristic acid, the different stearyl ester of Palmic acid, the different cetyl of isostearic acid, the different stearyl ester of isostearic acid, the own ester of isostearic acid, the isostearic acid ethyl ester, the isostearic acid isopropyl ester, isostearic acid octyl dodecanol ester (Octyldodecyl ォ Network チ Le De デシ Le), ethyl oleate, Ethyl linoleate, the linoleic acid isopropyl ester, octyl dodecyl myristate, octyl palmitate, different octyl palmitate, octyl stearate, Standamul 7061, butyl stearate, Octanoic acid, hexadecyl ester, decyl oleate, Cetiol, oleic acid octyl dodecanol ester, lauric acid hexyl ester, the different stearyl ester of lauric acid, different octyl pelargonate, different n-nonanoic acid isotridecanol, neopentanoic acid octyl dodecanol ester, the sad hexadecanol ester of dimethyl, the misery basic lauryl alcohol ester of dimethyl-octa, octyl hydroxystearate, Lauryl lactate, Tetradecyl lactate, lactic acid octyl dodecanol ester, citric acid octyl dodecanol ester, single isostearic acid two glyceride, benzoic acid alkane ester, monoester oils such as cinnamic acid UV absorbent such as p-methoxycinnamic acid 2-Octyl Nitrite; Two sad DOPCP, two capric acid DOPCP, N-lauroyl-L-glutamic acid two (plant sterol 2-octyl dodecanol) ester, N-lauroyl-L-glutamic acid two (cholesterol octyl dodecanol) ester, Ethylene glycol dicaprylate, two oleic acid glycol esters, two oleic acid propylene glycol esters, two sad propylene glycol esters, two (sad capric acid) propylene glycol ester, two isostearic acids, two glyceride, malic acid two different stearyl esters, (isostearic acid myristic acid) glyceride, dioctyl succinate, diisobutyl adipate, dioctyl adipate, ethyl sebacate, Dermol DIPS, di-n-octyl sebacate, dibasic acid esters oils such as the different cetyl of 12-stearoyl hydroxy stearic acid; Three ester oils such as tricaprylin, three sad trihydroxy methyl propyl ester, three (sad capric acid) glyceride, three glyceryl isostearates, three isostearic acids, two glyceride, tricaprylin, triethyl citrate, trioctyl lemon acid, citric acid three different cetyl, citric acid trioctylphosphine lauryl alcohol ester; Four ester oils of four oleic acid, two glyceride, citric acid acetyl triethyl, citric acid acetyl tributyl, four sad tetramethylolmethanes, four isostearic acid tetramethylolmethanes, four isostearic acids, two glyceride; As the mixture natural oil of monoester oil～three ester oils, can enumerate olive oil, Testa oryzae oil, Semen Tritici aestivi germ oil, macadamia oil, American Avocado Tree oil, almond oil, safflower oil, soybean oil, Semen Maydis oil, Oleum Brassicae campestris, Oleum Cocois, ermine oil (mink oil), Jojoba wet goods.

Wherein, the easier performance of monoester oil, dibasic acid esters oil, three ester oils and natural oil improves the effect of emulsion stability of the present invention, so preferred.And, consider from usability, be preferably molecular weight at the material of 350～1000 scopes or from the natural grease of plant extract.And, the more preferably different tridecane ester of myristic acid, octyl dodecyl myristate, two sad neopentyl glycols, two isostearic acids, two glyceride, (isostearic acid myristic acid) glyceride, N-lauroyl-L-glutamic acid two (plant sterol 2-octyl dodecanol) ester, N-lauroyl-L-glutamic acid two (cholesterol octyl dodecanol) ester, macadamia oil, olive oil, Jojoba oil.

Composition (A) can use more than one, and the content in the O/W emulsion composition of the present invention is preferably 0.05～70 weight %, more preferably 0.1～50 weight %, 0.5～30 weight % more preferably.

Moreover, except that composition (A), also can contain the oiliness composition of liquid, for example hydrocarbon ils such as liquid paraffin, squalane in the oil phase; Silicone oils such as methyl polysiloxane, methyl cyclopolysiloxane, octamethyltrisiloxane, methyl phenyl silicone, methylhydrogenpolysi,oxane, higher alcohol modified silicone oil, alkyl-modified silicone oil, amino modified silicone; Fluorocarbon oils such as PFPE, perfluoroalkyl ethers silicone etc.

Emulsification composition of the present invention is with respect to all oil phase total amounts, and the shared ratio of liquid oil sexual element that contains composition (A) is 5～90 weight %, be preferably 15～80 weight %, 35～65 weight % more preferably.As long as in this scope, just can obtain good surface appearance and excellent emulsion stability.

In addition, except that composition (A), (B), (D) and (E), also contain above-mentioned hydrocarbon ils, silicone oil, fluorocarbon oil etc. in the oil phase.

The sphingosine class of composition used in the present invention (B) is the material with above-mentioned general formula (1) expression.

In the formula, R ¹Represent available hydroxyl, carbonyl or the amino carbon number 4～30 that replaces, be preferably that hydroxyl can replace straight chain, side chain or the cyclic saturated or undersaturated alkyl of carbon number 7～22.Wherein be preferably the alkyl of the straight or branched of the alkyl of the straight or branched of carbon number 10～20, carbon number 10～20 that Y side end has hydroxyl, when being branched alkyl, side chain is the alkyl of methyl branch etc.Be preferably tridecyl, myristyl, pentadecyl, cetyl, stearyl, 1-hydroxyl tridecyl, 1-hydroxyl pentadecyl, isocetyl, iso stearyl particularly.

Y represents methylene (CH ₂), methine (CH) or oxygen atom any.

X ¹, X ²And X ³Difference independent and expression hydrogen atom, hydroxyl or acetate; X ⁴Expression hydrogen atom, acetyl group or glyceryl or form the substituent group of carbonyl with contiguous oxygen atom.Wherein, be preferably X ¹, X ²And X ³In 0～1 be hydroxyl, all the other are hydrogen atom and X ⁴Be hydrogen atom.In addition, when Y is methine, X ¹And X ²Any be hydrogen atom, another does not exist; Moreover, work as X ⁴When forming carbonyl, X ³Do not exist.

R ²And R ³Difference independent and expression hydrogen atom, hydroxyl, methylol or acetate methyl, R ³Hydrogen atom more preferably.

Moreover a represents 2 or 3 numeral, and when a was 2, R represented R ⁴And R ⁵, when a was 3, R represented R ⁴, R ⁵And R ⁶

R ⁴, R ⁵And R ⁶Independent respectively is hydrogen atom or amidino groups, and expression can have the saturated or unsaturated alkyl of the straight or branched of the substituent total carbon atom number 1～8 that is selected from hydroxyl, hydroxy alkoxy base, alkoxyl and acetate.Here, as commutable hydroxy alkoxy base in the alkyl, the hydroxy alkoxy base of the straight or branched of preferred carbon number 1～7.Moreover, as alkoxyl, the alkoxyl of the straight or branched of preferred carbon number 1～7.As R ⁴, R ⁵And R ⁶, for example can enumerate and be selected from hydrogen atom; Straight or branched alkyl such as methyl, ethyl, propyl group, 2-ethylhexyl, isopropyl; Alkenyl such as vinyl, pi-allyl; Amidino groups; Methylol, 2-ethoxy, 1,1-dimethyl-2-ethoxy, 2-hydroxypropyl, 2,3-dihydroxypropyl, 2-hydroxyl-3-methoxy-propyl, 2,3,4,5,6-pentahydroxy-hexyl, 1,1-two (methylol) ethyl, 2-(2-hydroxyl-oxethyl) ethyl, 2-methoxy ethyl, 1-methyl-2-ethoxy, 3-hydroxypropyl, 3-methoxy-propyl, 1, the alkyl of the total carbon atom number 1～8 of 1～6 replacement of 1-two (methylol)-hydroxyl, hydroxy alkoxy base and alkoxyls such as 2-ethoxy.

Wherein, be preferably selected from hydrogen atom or methyl, 2-ethoxy, 1,1-dimethyl-2-ethoxy, 1,1～3 commutable alkyl of hydroxyl such as 1-two (methylol) ethyl, 2-(2-hydroxyl-oxethyl) ethyl and hydroxy alkoxy base.

As sphingosine class, preferably use the natural or natural type sphingosine class of following general formula (2) expression and derivant thereof (below be designated as " natural type sphingosine ") or have a doubtful type that sphingosine constructs (below be designated as " doubtful type sphingosine ") with general formula (3) expression with general formula (1) expression.

(I) the natural type sphingosine of representing with general formula (2):

In the formula, R ¹¹Straight chain, side chain or the cyclic saturated or undersaturated alkyl of representing the carbon number 7～19 that available hydroxyl replaces; Y ₁Expression methylene or methine; X ¹¹, X ¹²And X ¹³Difference independent and expression hydrogen atom, hydroxyl or acetate; X ¹⁴Represent hydrogen atom, or form carbonyl, still, work as Y with contiguous oxygen atom ₁During for methine, X ¹¹And X ¹²Any the expression hydrogen atom, another does not exist, and works as X ¹⁴When forming carbonyl, X ¹³Do not exist; R ¹²Expression hydroxyl or acetate methyl; A R ₁Independent respectively is hydrogen atom or amidino groups, and also expression can have the saturated or unsaturated alkyl of the straight or branched of the substituent total carbon atom number 1～4 that is selected from hydroxyl, hydroxy alkoxy base, alkoxyl and acetate; A represents 2 or 3; Dotted line is represented also can be unsaturated bond.

Here, as R ¹¹, straight chain, side chain or the cyclic saturated or undersaturated alkyl of preferred carbon number 7～19, the more preferably saturated or undersaturated alkyl of the straight chain of carbon number 13～15.A is preferably 2, R ₁Independence and be preferably hydrogen atom or the alkyl of the straight or branched of carbon number 1～4 respectively.

As natural type sphingosine, can enumerate natural sphingosine, dihydrosphingosine, phytosphingosine, nerve sheath diene (sphingadienine), dehydrosphingosine, dehydrogenation phytosphingosine and their N-acetyl body, N-alkyl body (for example N-methyl body) etc. particularly with general formula (2) expression.

These sphingosines both can use the optically active body of natural type (D (+) body), also can use the optically active body of non-natural type (L (-) body), also can use the mixture of natural type and non-natural type.The relative stereoscopic configurations of above-claimed cpd both can be that the stereoscopic configurations of natural type also can be the stereoscopic configurations of non-natural type in addition, can also be the stereoscopic configurations of their mixture.

Be preferably phytosphingosine (INCI name especially; 8th Edition) and the material of representing with following general formula.

In the formula, m represents 5～17,1 expression 1～13

They can be from any of natural extract and chemical compound, can use commercially available material.

As the commercially available product of natural type sphingosine, for example can enumerate D-sphingosine (4-sphingol) (SIGMA-ALDRICH society), DS-dehydrosphingosine (DOOSAN society), dehydrosphingosine (COSMOFARM society).

(II) the doubtful type sphingosine of representing with general formula (3):

In the formula, R ¹³Straight chain, side chain or the cyclic saturated or undersaturated alkyl of representing the carbon number 10～22 that available hydroxyl replaces; X ¹⁵Expression hydrogen atom, acetyl group or glyceryl; A R ₂Difference independent and expression hydrogen atom or amidino groups, also expression can have the saturated or unsaturated alkyl of the straight or branched of the substituent total carbon atom number 1～8 that is selected from hydroxyl, hydroxy alkoxy base, alkoxyl and acetate; A represents 2 or 3 numeral.

Here, as R ¹³, the different branched alkyl of preferred carbon number 14～20, more preferably iso stearyl.The iso stearyl that the isooctadecanol of the by-product when the more preferably comfortable in the future manufacturing of iso stearyl is used from the dimer acid of the fatty acid of vegetable and animals oils obtains as raw oil.

Moreover, when a is 2, R ₂Expression R ¹⁴And R ¹⁵, when a is 3, R ₂Expression R ¹⁴, R ¹⁵And R ¹⁶

R ¹⁴, R ¹⁵And R ¹⁶For example can enumerate and be selected from hydrogen atom; Straight or branched alkyl such as methyl, ethyl, propyl group, 2-ethylhexyl, isopropyl; Alkenyl such as vinyl, pi-allyl; Amidino groups; Methylol, 2-ethoxy, 1,1-dimethyl-2-ethoxy, 2-hydroxypropyl, 2,3-dihydroxypropyl, 2-hydroxyl-3-methoxy-propyl, 2,3,4,5,6-pentahydroxy-hexyl, 1,1-two (methylol) ethyl, 2-(2-hydroxyl-oxethyl) ethyl, 2-methoxy ethyl, 1-methyl-2-ethoxy, 3-hydroxypropyl, 3-methoxy-propyl, 1, the alkyl with substituent total carbon atom number 1～8 of 1-two (methylol)-hydroxyl, hydroxy alkoxy base and alkoxyls such as 2-ethoxy.

Wherein be preferably R ¹⁴And R ¹⁵Any be hydrogen atom, another is a 2-ethoxy, 1,1-dimethyl-2-ethoxy, 1, the secondary amine of 1-two (methylol) ethyl, 2-(2-hydroxyl-oxethyl) ethyl.

As doubtful type sphingosine, preferred R ¹³Be iso stearyl, X ¹⁵Be hydrogen atom, R ¹⁴Be hydrogen atom, R ¹⁵For being selected from 2-ethoxy, 1,1-two (methylol) ethyl, 1, the sphingosine of the alkyl of 1～3 replacement of hydroxyl such as 1-dimethyl-2-ethoxy or 2-(2-hydroxyl-oxethyl) ethyl and hydroxy alkoxy base.

As the concrete example of doubtful type sphingosine, can enumerate following doubtful type sphingosine (i)～(iv).

Composition (B) can use more than one, the content of O/W emulsion composition of the present invention be preferably 0.001～10 weight %, more preferably 0.005～5 weight %, further be preferably 0.01～3 weight %, because obtain more excellent usability, so preferred.

The inventor thinks that be selected from mineral acid and the organic acid acid compound of carbon number below 5 of composition used in the present invention (C) carry out neutralization reaction by the amino with the sphingosine class of composition (B) and form salt, and the sphingosine class is worked as surfactant by cationization.The salt of sphingosine class has specific chemical compound structure usually, uses infrared ray to inhale optical spectroscopy or proton magnetic resonance (PMR) optical spectroscopy etc. and can confirm.

The pH that composition (C) is preferably at 25 ℃ 0.1mol/L aqueous solution is for greater than 1 less than 7, more preferably pH is 1～6.5 material.

As the mineral acid in the composition (C), can enumerate phosphoric acid, hydrochloric acid, nitric acid, sulphuric acid, perchloric acid, carbonic acid etc.

As organic acid, can enumerate monocarboxylic acids such as formic acid, acetic acid, propanoic acid, butanoic acid, isopropylformic acid., valeric acid; Dicarboxylic acids such as succinic acid, phthalic acid, fumaric acid, ethanedioic acid, malonic acid, 1,3-propanedicarboxylic acid; Hydroxy carboxylic acid such as glycolic, citric acid, lactic acid, acetone acid, malic acid, tartaric acid; Aminoacid such as glutamic acid, aspartic acid etc.

As composition (C), preferably phosphoric acid, hydrochloric acid, succinic acid, citric acid, lactic acid, glutamic acid, aspartic acid etc., more preferably lactic acid, glutamic acid, aspartic acid etc.

Composition (C) can use more than one, and the content of O/W emulsion composition of the present invention is preferably 0.001～10 weight %, more preferably 0.005～5 weight %, 0.01～3 weight % more preferably.

Moreover in order to make the amine cationization of (B) sphingosine class, the content of composition (C) is preferably more than 0.3 mole with respect to 1 mole of composition (B), and more preferably 0.3～5 mole further is preferably 0.5～3 mole.For example, preferably under 25 ℃ be 2～6 (after the revisals of phthalic acid titer, measuring) with HORIBApH Meter F-22 with the pH of the blended aqueous solution of mole such as composition (B).

In O/W emulsion composition of the present invention, composition (A), (B) and quality ratio (C) (A)/((B)+(C)) is 0.1～100, consider from the aspect that has good stability, be preferably 0.5～70, more preferably 0.5～50, more preferably 2～50.

In the present invention, the cholesterol or the plant sterol of composition (D) are prevalent in the surface with sphingosine class and acid compound, work as emulsion adjuvant, even so think and under low temperature and high temperature are preserved, also the surface of oil phase and water can be remained on stable status, and improve emulsion stability.

Can use cholesterol and plant sterol simultaneously as composition (D).The content of the composition in the O/W emulsion composition of the present invention (D) is preferably 0.05～20 weight %, for obtaining more excellent stability and sense of touch, more preferably 0.1～15 weight %, further be preferably 0.2～10 weight %.

And with respect to all oil phase total amounts, the shared ratio of composition (D) is preferably 0.1～80 weight %, considers from improving the emulsion stability aspect, more preferably 0.5～60 weight %, 1～40 weight % more preferably.

In O/W emulsion composition of the present invention, composition (B), (C) and quality ratio (D) ((B)+(C))/(D) be preferably 0.001～100, consider more preferably 0.005～50, more preferably 0.01～30 from the aspect that has good stability.

Moreover composition (A) and quality ratio (D) (A)/(D) are preferably 0.05～70, consider more preferably 0.1～30, more preferably 0.1～20 from the aspect that has good stability.

O/W emulsion composition of the present invention except that above-mentioned composition (A)～(D), also can contain 25 ℃ down for the oiliness composition of semisolid or solid, shaped as composition (E), can further improve emulsion stability.As being the oiliness composition of semisolid or solid, shaped down, for example, can enumerate higher alcohols such as stearyl alcohol, spermol, isooctadecanol, cetostearyl alcohol (cetostearyl), myristyl alcohol at 25 ℃; Senior fatty acids such as stearic acid, Palmic acid, myristic acid; Fatty acid esters such as isostearic acid cholesteryl ester, isostearic acid plant sterol ester, stearic acid stearyl ester, myristyl myristate, cetin; Vaseline, agnolin, ceresin (Ceresin), Cera Flava, Brazil wax, candelilla wax, hydrogenation Jojoba wet goods wax; The spy opens the diamide compound etc. of the following general formula of usefulness (4) expression of 2002-114666 communique record.

In the formula, R ²¹The independent respectively expression alkyl of the straight or branched of hydroxyl and/or the commutable carbon number 1～22 of alkoxyl, R ²²The bivalent hydrocarbon radical of the straight or branched of independent respectively expression carbon number 1～12, R ²³The bivalent hydrocarbon radical of expression carbon number 1～42 straight or branched.

As composition (E), consider the diamide compound that is preferably stearyl alcohol, spermol, stearic acid, isostearic acid cholesteryl ester, isostearic acid plant sterol ester, vaseline, candelilla wax, represents with above-mentioned general formula (4) from significantly improving effect of the present invention aspect.And, higher alcohols such as stearyl alcohol, spermol, cetostearyl alcohol more preferably.Moreover, by containing diamide compound (4), can improve the barrier functions such as transpiration of moistening effect, anti-sealing, usability is more excellent.

The inventor thinks that composition (E) suppresses the mobile of oil phase and improves emulsive stability.

Composition (E) can use more than one, the content of O/W emulsion composition of the present invention is preferably 0.01～40 weight %, consider from the excellent aspect of emulsion stability and usability, more preferably 0.05～20 weight %, 0.1～15 weight % more preferably.

The amount of the water of emulsification composition of the present invention is preferably 20～99 weight %, 40～99 weight % more preferably in full the composition.Beyond aqueous phase dewaters, also can contain the composition that other is dissolved in water, for example polyhydric alcohol such as 1,3 butylene glycol, propylene glycol, dipropylene glycol, glycerol; Lower alcohol such as ethanol, isopropyl alcohol; Wetting agents such as Sorbitol, Polyethylene Glycol, betanin, xylitol, trehalose, carbamide, aminoacid; Water soluble polymers such as xanthan gum, hydroxyethyl-cellulose, methylcellulose, hydroxypropyl guar gum; Plant extracts such as eucalyptus extracts, Fucus Vesiculosus extract, Thujopsis dolabrata extract, chamomile extract, Radix Sangusorbae extract, tea extract; Water solublity drug effect agent such as magnesium ascorbyl phosphate salt, glycyrrhetate, vitamin; Metallic salt such as calcium chloride, magnesium sulfate; PH buffer agents such as citric acid, succinic acid, trisodium citrate; Antiseptic such as methyl parahydroxybenzoate, dehydro sodium acetate, phenoxyethanol etc.

Except that above-mentioned composition, also contain employed composition in common cosmetic or pharmaceuticals in the O/W emulsion composition of the present invention, for example organic powders such as cellulose powder, nylon powder, porous matter cellulose powder, porous matter nylon powder; Silicone powder such as cross-linking type silicone powder, cross-linking type methyl polysiloxane; Inorganic particles such as anhydride silica, zinc oxide, titanium oxide, ferrum oxide; Freshener such as menthol, Camphora; Ultraviolet screening agent, antioxidant, spice, antibacterial, pigment etc.

In O/W emulsion composition of the present invention, do not need to be used for emulsive surfactant, but, can contain as required yet for the purposes such as dispersion of the stabilisation of active ingredient, powder body etc.

O/W emulsion composition of the present invention for example can be made by the following method, promptly, composition (A), (B), (D) and the composition (E) that adds as required are heated to the above dissolving of fusing point as oil phase, in the time of holding temperature to wherein slowly adding aqueous solution and the emulsifying that in advance composition (C) is dissolved in water.

In addition, O/W emulsion composition of the present invention is surveyed down directly periodic pH at 25 ℃ and is preferably 3～7, and more preferably 4～6.

O/W emulsion composition of the present invention can be used as cosmetic, pharmaceuticals, balneation agent, wipes away agent, head clearing agent etc. clearly.For example be preferably used as foundation make up material such as astringent, emulsion, facial cream, beautifying liquid; Cosmetics such as bottom cosmetic, foundation cream, screening flaw liquid, eye shadow, mascara; Hair such as hair cream, conditioning hairdressing is expected with making up.

Embodiment

Embodiment 1～7, comparative example 1～4

Utilize the O/W emulsion composition of forming shown in the following method manufacturing table 1.The emulsification composition that obtains is carried out the evaluation of outward appearance, storage stability and usability.Moreover, mix each composition, at 25 ℃ of pH that directly measure compositions down.Also expression in table 1 of result.

(manufacture method)

After composition (1)～(10) were heated to 80～90 ℃ of dissolvings, the limit was stirred (300r/min) limit and is added in advance in addition material with 80～90 ℃ of even heating dissolving composition (11)～(14).After homogenizer was installed, cool to room temperature obtained O/W emulsion composition while stirring.

(evaluation methodology)

(1) outward appearance:

By 10 experts' sense evaluation, estimate each compositions whether glossy, whether be uniform state.Evaluation criterion: " gloss of outward appearance " is very good: 5 points, good: 4 points, common: 3 points, slightly bad: 2 points, bad: 1 point, 10 experts' equalization point be expressed as ◎ more than 4.5, more than 3.5 4.5 following tables be shown zero, more than 2.5 3.5 below for △, below 2.5 be *.

(2) storage stability:

Each O/W emulsion composition is filled in the 50mL vial, respectively leaving standstill under 40 ℃, 25 ℃, 5 ℃ preserve 3 months after, with the naked eye and observation by light microscope, compare with the emulsified state after the firm modulation, estimate with following standard.

◎: do not change

Zero: only have a bit to change (under optical microscope, seeing synthetic one of granule).

△: see slightly change (some oil slick or milk, gelation are slightly only arranged).

*: confirm to change obviously (see separating of oil, occur milk, gelation).

(3) usability:

" quality of the fused property when being coated on the skin ", " having or not oiliness during coating ", " skin after the coating has or not the sense of being clamminess " when 10 experts carry out the sense evaluation and use each O/W emulsion composition, judge with following standard.

◎: be evaluated as good (very) more than 9

Zero: 7～be evaluated as more than 8 good (very)

△: be evaluated as good (very) more than 4～6

*: be evaluated as good (very) below 3

Table 1

	Composition (weight %)	Embodiment							Comparative example
													1	2	3	4	5	6	7	1	2	3	4
		A	(1) two capric acid DOPCP	0.5	3	5	3		2	1	3	3												0.05	3
(2) octyl dodecyl myristate														5		3
			B	(3) doubtful type sphingosine ^*1		0.04	0.2		3	0.5	0.1												0.6	1	0.2
(4) phytosphingosine	0.1													1	2
				D	(5) cholesterol	0.2	0.5	10	0.25		1.5	1										0.5		0.5	1
(6) plant sterol		0.5												2			0.5
					E	(7) vaseline				5		2									5
(8) hard ester alcohol				2										1	2
							(9) squalane				5	2								1		1	1
(10) methyl polysiloxane (20cs)			2	15	2								1					15
							C	(11) L-glutamic acid	0.1	0.02									1.3	0.2	0.05		0.3	0.4	0.1
(12) lactic acid			0.1	0.5	1
									(13) methyl parahydroxybenzoate	0.2	0.2	0.2						0.2	0.2	0.2	0.2	0.2	0.2	0.2	0.2
(14) Purified Water	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus						Surplus	Surplus	Surplus	Surplus
									Add up to		100	100					100	100	100	100	100	100	100	100	100
Ratio (weight %) with respect to the liquid oil of all oil phase total amounts		63	74	54	74	50	44	11					80	87	3.2	94
									The ratio of A/ (B+C)		2.5	50					33	2	0.4	2.9	6.7	-	3.3	3.6	10
D shared ratio (weight %) in all oil phase total amounts		25	25	45	0.8	14	17	11					20	0	32	5.2
										Outward appearance	◎	○					○	△	◎	◎	◎	×	△	○	△
	PH value	4	5	4	4	5	6	5					7	5	5	5

Storage stability: 40 ℃, three months

◎

△

○

◎

-

×

○

×

25 ℃, three months

◎

○

◎

-

×

○

△

5 ℃, three months

◎

○

△

○

◎

-

△

Usability (the fused property when being coated on the skin)

◎

○

◎

△

-

×

(having or not oiliness during coating)

◎

○

◎

○

-

×

△

×

(skin after the coating has or not the sense of being clamminess)

◎

○

△

◎

○

-

△

×

△

^*1: in general formula (3), R ¹³Be iso stearyl, X ¹⁵For hydrogen atom, a are 2, R ¹⁴Be 2-ethoxy, R ¹⁵Be hydrogen atom

As shown in Table 1: the O/W emulsion composition of embodiment 1～7 is outward appearance, the storage stability under 40 ℃, 25 ℃ and 5 ℃, compositions that usability is good.Do not contain composition (B) and comparative example (C) 1 oil when just modulating the back and do not have uniformly emulsify.The comparative example that does not contain composition (D) is 2 lackluster, the stability or the usability of appearance poor, emulsified state are also poor.It is poor in the emulsion stability under the cryopreservation less than 5% comparative example 3 to contain the ratio that the oiliness composition of the liquid of composition (A) occupied with respect to full oil phase total amount, and usability has the sense of being clamminess, fused property poor.Moreover the shared ratio of the oiliness composition of liquid surpasses the outward appearance of 90% comparative example 4 or emulsion stability is poor, usability also has oiliness and the sense of being clamminess is arranged.

Embodiment 8 (astringent)

Utilize the astringent of forming shown in the following method manufacturing table 2.The pH of the astringent that obtains be 4 and outward appearance, stability and usability good.

(manufacture method)

The material that dissolves composition (4)～(12), (14) in advance with 80～90 ℃ of even heating 80～90 ℃ of heating for dissolving, is added in composition (1)～(3) when stirring (300r/min).After homogenizer is installed, be cooled to 35 ℃ in the time of stirring, behind the interpolation composition (13), cool to room temperature obtains astringent.

Table 2

(composition)		(weight %)
			?B	(1) phytosphingosine (COSMOFARM society)	0.2
?D	(2) plant sterol (the biochemical society of TAMA)	0.2
			?A	(3) the different tridecane ester of myristic acid	0.5
	(4) vaseline	5
				(5) trehalose	1
	(6) dipropylene glycol	3
				(7) hydroxypropyl guar gum	1

?C	(8) L-aspartic acid	0.1
			(9) aethyl parabenum	0.1
	(10) Althaea rosea (L.) Cavan. extract	0.1
			(11) grapefruit abstract	0.1
	(12) Thujopsis dolabrata extract	0.5
			(13) ethanol	0.2
	(14) Purified Water	Balance

Embodiment 9 (emulsion)

Utilize the emulsion of forming shown in the following method manufacturing table 3.The pH of the emulsion that obtains be 6 and outward appearance, stability and usability good.

(manufacture method)

Composition (1)～(9) 80～90 ℃ of heating for dissolving, are added on the material of 80～90 ℃ of heating for dissolving compositions (10)～(18) when stirring (300r/min).With after the homogenizer emulsifying, cool to room temperature obtains emulsion while stirring after adding.

Table 3

(composition)		(weight %)
			?B	(1) phytosphingosine (COSMOFARM society)	0.4
?A	(2) (isostearic acid myristic acid) glyceride	2
			?D	(3) plant sterol (reason is ground Vitamin society)	1
	(4) methyl polysiloxane (10cs)	10
			?E	(5) isostearic acid plant sterol ester	2
?A	(6) N-lauroyl-L-glutamic acid two (plant sterol 2-octyl dodecanol) ester	3
			?E	(7) spermol	1
	(8) PFPE ^*2	1
			?E	(9) Palmic acid	0.5
	(10) glycerol	10

(11) betanin (society of Asahi Chemical Industry)	1
		?C	(12) lactic acid	0.1
(13) Radix Hamamelidis Mollis extract	0.3
			(14) Althaea rosea (L.) Cavan. extract	0.2
(15) eucalyptus extracts	0.2
			(16) Cortex Phellodendri extract	0.1
(17) nipagin	0.2
			(18) Purified Water	Balance

^*2:FOMBLIN HC (Ausimont USA society)

Embodiment 10 (facial cream)

Utilize the facial cream of forming shown in the following method manufacturing table 4.The pH of the facial cream that obtains be 6 and outward appearance, stability and usability good.

(manufacture method)

Composition (1)～(11) are heated to 80～90 ℃ and stir and to make it dissolving, are added on the material of 80～90 ℃ of heating for dissolving compositions (12)～(22) when stirring (300r/min).Add the back homogenizer is installed, cool to room temperature obtains facial cream while stirring.

Table 4

(composition)		(weight %)
			?B	(1) doubtful type sphingosine ^*1	0.2
?B	(2) phytosphingosine (COSMOFARM society)	0.3
			?A	(3) two isostearic acids two glyceride	3
?A	(4) olive oil	5
			?E	(5) diamide compound ^*3	2
?E	(6) stearyl alcohol	2
			?D	(7) plant sterol (the biochemical society of TAMA)	1
?D	(8) cholesterol	1

?E	(9) isostearic acid cholesteryl ester	2
			?E	(10) stearic acid	0.3
	(11) methyl polysiloxane (50cs)	5
				(12) glycerol	15
?C	(13) L-glutamic acid	0.2
				(14) Macrogol 1540 (Sanyo changes into society)	3
	(15) 1,3 butylene glycol	2
				(16) phenoxyethanol	2
	(17) nipagin	0.1
				(18) royal jelly extract	0.3
	(19) Fucus Vesiculosus extract	0.1
				(20) Thujopsis dolabrata extract	0.1
	(21) spice	Trace
				(22) Purified Water	Balance

^*3: the spy opens the chemical compound that the 2002-114666 communique is put down in writing

Embodiment 11 (beautifying liquid)

Utilize the beautifying liquid of forming shown in the following method manufacturing table 5.The pH of the beautifying liquid that obtains be 5 and outward appearance, stability and usability good.

(manufacture method)

Composition (1)～(9) are heated to 80～90 ℃ make it dissolving, be added on the material of 80～90 ℃ of heating for dissolving compositions (10)～(21) when stirring (300r/min).Add the back homogenizer is installed, cool to room temperature obtains beautifying liquid while stirring.

Table 5

(composition)

(weight %)

?B	(1) doubtful type sphingosine ^*1	0.8
			?A	(2) macadamia oil	4
?A	(3) myristyl myristate	2
				(4) tocopherol	0.1
	(5) methyl polysiloxane (2cs)	10
			?A	(6) Jojoba oil	3
?D	(7) liquid paraffin	1
				(8) plant sterol (the biochemical society of TAMA)	3
	(9) beta-carotene	Trace
				(10) dipropylene glycol	5
	(11) hyaluronic acid	0.2
				(12) hydroxypropyl emthylcellulose ^*4	0.6
	(13) magnesium ascorbyl phosphate	0.2
			?C	(14) L-glutamic acid	0.4
	(15) disodium edetate	0.05
				(16) nipagin	0.2
	(17) tea extract	0.1
				(18) Radix Sangusorbae extract	0.2
	(19) Thujopsis dolabrata extract	0.5
				(20) chamomile extract	0.5
	(21) Purified Water	Balance

^*4:metolose 60SH-10000 (chemistry society of SHIN-ETSU HANTOTAI)

Embodiment 12 (sunscreen cream)

Utilize the sunscreen cream of forming shown in the following method manufacturing table 6.The pH of the sunscreen cream that obtains be 5 and outward appearance, stability and usability good.

(manufacture method)

With 80～90 ℃ of composition (1)～(10) heating and make it dissolving, the material that (300r/min) limit is added on 80～90 ℃ of heating for dissolving compositions (11), (12), (14)～(16) is stirred on the limit.Add the back homogenizer is installed, be cooled to 35 ℃ while stirring, behind the interpolation composition (13), cool to room temperature obtains sunscreen cream.

Table 6

(composition)		(weight %)
			?B	(1) doubtful type sphingosine ^*1	2
?E	(2) hydroxy stearic acid cholesteryl ester	2
				(3) methyl cyclopolysiloxane (five-membered ring)	15
?A	(4) p-methoxy cinnamic acid 2-Octyl Nitrite	5
			?A	(5) benzoic acid alkane ester (C12～15)	2
?D	(6) cholesterol	2
			?D	(7) plant sterol (the biochemical society of TAMA)	1
?E	(8) Cera Flava	3
			?E	(9) behenyl alcohol	3
	(10) methyl polysiloxane (10cs)	5
				(11) glycyrrhizic acid dipotassium	0.5
	(12) glycerol	5
				(13) ethanol	3
	(14) nipagin	0.2
			?C	(15) L-glutamic acid	1
	(16) Purified Water	Balance

Claims

1. an O/W emulsion composition is characterized in that, contains following composition (A), (B), (C) and (D):

(A) be the monoester oil of liquid, dibasic acid esters oil or three ester oils down at 25 ℃;

(B) the natural type sphingosine of representing with general formula (2):

In the formula, R ¹¹Straight chain, side chain or the cyclic saturated or undersaturated alkyl of representing the carbon number 7～19 that available hydroxyl replaces; Y ₁Expression methylene or methine; X ¹¹, X ¹²And X ¹³Independent respectively going up and expression hydrogen atom, hydroxyl or acetate; X ¹⁴Represent hydrogen atom, or form carbonyl, still, work as Y with contiguous oxygen atom ₁During for methine, X ¹¹And X ¹²Any the expression hydrogen atom, another does not exist, and works as X ¹⁴When forming carbonyl, X ¹³Do not exist; R ¹²Expression hydroxyl or acetate methyl; A R ₁Independent respectively is hydrogen atom or amidino groups, and also expression can have the saturated or unsaturated alkyl of the straight or branched of the substituent total carbon atom number 1～4 that is selected from hydroxyl, hydroxy alkoxy base, alkoxyl and acetate; A represents 2 or 3; Dotted line is represented to have unsaturated bond or is not had unsaturated bond;

Perhaps, the doubtful type sphingosine of representing with general formula (3):

In the formula, R ¹³Straight chain, side chain or the cyclic saturated or undersaturated alkyl of representing the carbon number 10～22 that available hydroxyl replaces; X ¹⁵Expression hydrogen atom, acetyl group or glyceryl; A R ₂Difference independent and expression hydrogen atom or amidino groups, also expression can have the saturated or unsaturated alkyl of the straight or branched of the substituent total carbon atom number 1～8 that is selected from hydroxyl, hydroxy alkoxy base, alkoxyl and acetate; A represents 2 or 3 numeral;

(C) be selected from the acid compound of phosphoric acid, hydrochloric acid, nitric acid, sulphuric acid, perchloric acid, carbonic acid, formic acid, acetic acid, propanoic acid, butanoic acid, isopropylformic acid., valeric acid, succinic acid, phthalic acid, fumaric acid, ethanedioic acid, malonic acid, 1,3-propanedicarboxylic acid, glycolic, citric acid, lactic acid, acetone acid, malic acid, tartaric acid, glutamic acid, aspartic acid;

(D) cholesterol or plant sterol;

With respect to all oil phase total amounts, the shared ratio of liquid oil sexual element that contains composition (A) is 5～90 weight %,

The content of composition (A) in O/W emulsion composition is 0.05～70 weight %,

The content of composition (B) in O/W emulsion composition is 0.001～10 weight %,

The content of composition (C) in O/W emulsion composition is 0.001～10 weight %,

And composition (A), (B) and quality ratio (C) (A)/((B)+(C)) is 0.1～100.

2. O/W emulsion composition as claimed in claim 1 is characterized in that:

With respect to all oil phase total amounts, the shared ratio of composition (D) is 0.1～80 weight %.

3. O/W emulsion composition as claimed in claim 1 or 2 is characterized in that:

Also containing (E) is down the oiliness composition of semisolid or solid, shaped at 25 ℃.

4. O/W emulsion composition as claimed in claim 1 or 2 is characterized in that:

5. O/W emulsion composition as claimed in claim 3 is characterized in that:

Composition (E) is the diamide compound with following general formula (4) expression,

In the formula, R ²¹The alkyl of the straight or branched of the carbon number 1～22 that available hydroxyl of independent respectively expression and/or alkoxyl replace, R ²²The bivalent hydrocarbon radical of the straight or branched of independent respectively expression carbon number 1～12, R ²³The bivalent hydrocarbon radical of expression carbon number 1～42 straight or branched.

6. O/W emulsion composition as claimed in claim 4 is characterized in that: